Polymerization in mass of ethylenic monomers and products produced thereby

ABSTRACT

A process of producing spherical particles of ethylenic monomers with controlled size distribution by prepolymerizing a portion of the monomer with turbulent agitation, transferring the prepolymerized monomer and mixing it with a large quantity of additional monomer and slowly and mild agitation polymerizing the bulk of the monomer. The quantity of monomer prepolymerized and the speed of agitation during prepolymerization serving as controls on the size distribution of the final product.

United States Patent Thomas Aug. 29, 1972 [54] POLYMERIZATION IN MASS OF 3,102,087 8/1963 Jobard ..260/92.8 ETHYLENIC MONOMERS AND 3,480,606 11/ 1969 Thomas ..260/92.8 PRODUCTS PRODUCED THERE FOREIGN PATENTS OR APPLICATIONS [72] Imam {f Clam! 1,382,072 11/1964 France ..260/92.8

rance [73] Assignee: Produits Chimiques Pechiney-Saint- Prim ry ExaminerJoseph L. Schofer Gobain, Paris, France Assistant Examiner-John A. Donahue, Jr. Filed: March 1966 Attorney-John L. Seymour and Arthur W. Dew [21] Appl. No.: 535,092 TRAC A process of producing spherical particles of ethylenic 3 Fm-eign Application priority Data monomers with controlled size distribution by prepolymerizing a portion of the monomer with turbu- March 17, 1965 France ..659561 lent agitation transferring the prepolymerized monomer and mixing it with a large quantity of addi- U-S- R, tiona] monomer and lowly and agitation polymerizing the bulk of the monomer. The quantity [5]] Int. Cl. ..C08f 1/04, C08f 3/30, C08f 15/30 of monomer prepolymerized and the Speed Of agita- [58] Field of Search ..260/87.5, 92.8, 87.1 tion during prepolymerization serving as controls on the size distribution of the final product. [56] References Cited 11 Claims, 4 Drawing Figures UNITED STATES PATENTS 2,961,432 ll/l960 Fikentscher et al. .....260/92.8

35 53 i I I I" l l f r} I 3o i 52 E a a a 9 M R w PATENTEI] M1629 um SHEET 1 BF 2 INVENTOR JEAN CLAUDE THOMAS n, J ATTORNEY minim-M29 I972 SHEET 2 BF 2 l I I 1 II II l l LL INVENTOR CLAUDE THOMAS 'Ti ETQ.

JEAN

ATTORNEY POLYMERIZATION IN MASS OF ETHYLENIC MONOMERS AND PRODUCTS PRODUCED THEREBY This invention relates in particular to the preparation of polyvinyl chloride in mass, that is to say in the absence of solvents and diluents, and in general to the polymerization in mass of ethylenic monomers the polymers of which are insoluble in their monomers. The term polymerization includes both homopolymerization and copolymerization.

It has been proposed in US. application Ser. No. 347,147, now abandoned, to polymerize such monomers to about 7 to percent of completion in an initial stage of turbulent agitation and to complete the polymerization to a selected end point, for instance around 70-75 percent, in a second stage removed from the first in time and place, with mild agitation. In the first stage the agitation is as turbulent as the nature of the process permits and in the second stage it is as mild as will maintain uniform conditions of temperature. The polymerization was carried out under conditions of temperature, pressure and catalysis favorable to the polymerization reaction. The temperatures employed, the corresponding pressures, and the catalysts used were typical of the prior art, as they are in the present invention.

It would be ideal to produce polyvinyl chloride grains all of one size and shape, for instance spheres 300 microns in diameter, but the prior art produced neither such sizes nor such shapes; the sizes were heterogeneous, from minute particles passing readily through a 100 micron screen to large aggregates greater than 630 microns in size. The shapes were flaky and irregular in every dimension. It was an object of the identified case, as it is an object of this one, to produce such polymers in regular spherical grains with an approach to uniformity of size. A breakthrough was obtained in US. application Ser. No. 97,982, now abandoned, wherein polyvinyl chloride was produced in spherical grains with a rough approximation of equal size. The case first identified exhibited a massive improvement in granulometry; the spherical grains constituted a larger percentage of the total production and variation in size was much reduced.

It is an object of the present invention to still further improve the granulometry (size, shape, and density) of ethylenic polymers by production in mass. It is also a particular object of this invention to improve the efficiency of the new process which is represented by these cases. Another object is to produce spherical grains of excellent granulometry by a new method.

The objects of the invention are accomplished by a method of polymerizing ethylenic monomers capable of polymerization in mass, which comprises subjecting such an ethylenic monomer in mass to conditions of temperature, pressure, and catalysis favorable to polymerization in a locus provided with agitation of sufficient violence to achieve major turbulence in the reaction mass until about 7 to 15 percent polymerization has been attained, the minute particles of polymer thus formed being suspended in liquid monomer, transferring the liquid suspension to another locus provided with mild agitation, mixing it with additional monomer, and containing the polymerization in mass under conditions favorable to growth of the particles, including agitation which is a function of good temperature control and achieves only minor turbulence, and conditions of temperature, pressure, and catalysis favorable to polymerization.

It will assist in comprehending the difference between the product of these cases and the product of the prior art to regard the product of the prior art as produced by random polymerization in random directions whereas the new product is produced by regular growth in all directions.

As the production of polyvinyl chloride is particularly valuable, this description will be directed mainly to its formation by the novel process and it is to be understood that this is a representative disclosure and that the process can be applied to other ethylenic monomers in which their polymers are insoluble. Examples include the comonomers hereinafter listed, vinyl compounds such as styrene and vinylidine chloride and acrylic monomers.

According to the present invention the polymerization includestwo stages, in the first of which the monomer, for instance vinyl chloride, is received in an autoclave under satisfactory conditions of temperature, pressure and catalysis and undergoes polymerization to 7 to 15 percent and preferably 8 to l0 percent, with turbulent agitation, the agitation in this stage being generally the more satisfactory as it is the higher. When this stage of polymerization has been reached and the solid polyvinyl chloride in minute particles is suspended in the liquid monomer, the suspension is flowed into another pool of monomer and the polymerization is continued with mild agitation. In this second stage the agitation is as mild as will produce a good temperature control of the entire reaction mass.

The catalysts employed are those which are normally used with the particular polymer involved. Lists are available in publications dealing withthe subject.

In the good practice of the present invention the quantity of monomer used in the first stage should be at least one-third by weight of the total quantity of monomer which is to undergo the reaction. The autoclave will receive, for example, one-third to one-half of the total charge, which will undergo the partial polymerization with turbulent agitation and the second autoclave will then receive the remainder of the monomer and the partly polymerized fluid and the total will undergo the second stage with mild agitation.

This process appears to involve a new phenomenon, the formation of minute seeds of polymer in the first stage, and the regular expansion of these seeds, by regular growth in all directions, to the formation of spherical grains of greater regularity in the second stage. There appears to be little if any new seed formation in the second stage, the second stage being devoted largely to the expansion of the seeds of the first stage.

The lower limit of one-third is not equatorial but a boundary of good practice when the monomer is vinyl chloride. It is possible to make positive or negative modifications as the function of the general reaction conditions and of the type of monomer being polymerized. In particular, the degree of turbulence in the first stage, a measure of which is the speed of the agitator in the autoclave, has an important effect as the greater the turbulence, the higher the speed of agitation, the greater the number of minute particles formed. This, in turn, has a determinative elfect on the average size of the spherical grains which are produced.

For general conditions relating to polymerization which are applicable to the present case French Pat. No. 1,357,736 may be consulted.

The following examples illustrate the invention. For better comprehension of what follows, the drawings illustrate the types of apparatus employed.

FIG. 1 illustrates a prepolymerizer 30 with inlet 32 and outlet 33 to a water jacket 31 which may be used for heating and cooling the contents of the autoclave. A cover is removable and is furnished with a heating and cooling coil served through inlet 36 and outlet 37. Ports 38, 39, and 40, appropriately valved, permit the filling, discharge and servicing of the contents of the autoclave. A motor M mounted on the cover drives an impeller 41. Valve 46 allows the contents of the autoclave to flow through pipe 44 and valves 47, 48 to a large autoclave which is of known type comprising a rotary cylinder driven from motor M through gears S and containing a line of balls which fluidize the polymer by rolling through it.

FIG. 2 is a vertical section through a horizontal autoclave of fixed type provided with helical agitators having inner and outer, oppositely pitched blades mounted on a shaft 58 which is appropriately driven. This autoclave is connected to the prepolymerizer by pipe 57 and valve 56.

FIGS. 3 and 4 are vertical sections through similar autoclaves, connected to the prepolymerizer, in which stirring is accomplished by full length or short length stirrers of paddle type.

Each of these types of apparatus has its own characteristics of operation which will be described in the following examples.

EXAMPLE 1 (Comparative Example) In the application identified above, there is described the polymerization of vinyl chloride in mass, in two steps of prepolymerization and final polymerization, in which the prepolymerization was carried out on the totality of the monomer. The present example is of that type.

A vertical prepolymerizer, similar to that in the drawings, of 200 1., in stainless steel, provided with a turbine agitator 180 mm. in diameter received 187 kg. of vinyl chloride and 30.6 g. (0.018 percent of the weight of the monomer) of azodiisobutyronitrile (ADBN) as a catalyst, after the apparatus had been purged with 17 kg. of vinyl chloride. The turbine was driven at 710 r.p.m. throughout the test. The temperature was raised rapidly to 62 C. and the pressure stabilized itself at 9.3 bars in the prepolymerizer.

After 3 hours the mixture of monomer and polymer contained between 7 and percent of polymer, and it was transferred to an autoclave of 500 1. capacity of the type shown in FIG. 2, this autoclave having been purged with kg. of vinyl chloride monomer. The transfer took less than a minute. The valves were closed and the agitator was rotated at 8 r.p.m. the temperature of the reaction mass was kept at 62 C., corresponding to 9.3 bars. The operation continued for 12 hours for a total of 15 hours. The yield was 72 percent of a polymer powder having a K value of 62 and an apparent density of 0.58. Its granulometry was:

TABLEI Screen apertures inmicrons 630 500 400 315 250 200160 %fallthrough 99.5 99 98 97 96 94 49 l Ninety six percent was smaller than 250 microns, 94 percent smaller than 200 microns and 49 percent smaller than 160 microns.

EXAMPLE 2 (This Invention) The apparatus was similar to that described in Example 1. A prepolymerizer received 100 kg. of vinyl chloride after purging and 18 g., 0.018 percent, ADBN catalyst. The temperature rose rapidly to 62 C. and the internal pressure was 9.3 bars.

After 3 hours of prepolymerization, between 7 and 15 percent of the polymer had formed and the mass was flowed into 100 kg. of vinyl chloride, containing 18 g. of ADBN, in the autoclave of FIG. 2. The transfer took less than a minute. The agitator in the cylindrical autoclave was rotated at 8 r.p.m., the temperature was 62 C. and the pressure was 9.3 bars. Polymerization continued 12 hours, for a total of 15 hours. The yield was 64.6 percent of a powder having a K value of 62 and an apparent density of 0.57. The granulometry is as follows:

TABLE II Screen apertures in microns 630 500 400 315 250 200 160 100 %fallthrough 97 97 96 96 95 91 3 1 It will be observed that 49 percent of sizes less than 160 microns were separated in the first examples above. Eighty-eight percent of the particles were between 160 microns and 200 microns and this is a substantial advantage for some uses, in the last example.

EXAMPLE 3 The apparatus was the same as in Examples 1 and 2. Only one-third of the monomer was subjected to prepolymerization. Seventy-five kg. of vinyl chloride were admitted to the purged prepolymerizer with 13.5 g., 0.018 percent, of ADBN. The agitator ran at 710 r.p.m., the temperature was 62 C. and the pressure 9.3 bars.

After 3 hours the partly polymerized reaction mass was flowed into the cylindrical autoclave which contained kg. of vinyl chloride monomer and 27 g., 0.018%, of ADBN. The transfer took less than a minute. The agitation was at 8 r.p.m., the temperature at 62 C. and the relative internal pressure 9.3 bars. Polymerization was for 12 hours for a total of 15 hours. The yield was 70.4 percent of a polymer having a K value of 62 and an apparent density of 0.54. The granulometry was:

TABLEIII Screen apertures in microns 630 500 400 315 250 200 100 %fallthrough 100 99 98 97 95 20 7 1 The granulometry is substantially different from the preceding examples, 75 percent of the particles being between 200 and 250 microns, where only 4 percent were in this size in the product of Example 2 and only 2 percent in the product of Example 1. It is thus apparent that the process makes it possible to produce particles of chosen granulometry. In each of these cases the products were tiny spheres.

EXAMPLE 4 The purged prepolymerizer of Example 1 received 75 kg. of vinyl chloride and 13.5 g. of ADBN. The temperature rose rapidly to 62 C. and the pressure to 9.3 bars.

After 3 hours the reaction mass was transferred to the cylindrical autoclave and charged with 27 g. of ADBN. The valve between the autoclaves was closed and 165 kg. of the same monomer were pumped into the prepolymerizer at 62 C. and used to rinse that vessel. The rinsed polymer was immediately transferred to the cylindrical autoclave and the polymerization continued at 62 C. for 12 hours 30 minutes withagitation at 8 r.p.m. The yield was 69.6 percent of the polymer having a K value of 62 and an apparent density of 0.55. Its granulometry was:

TABLEIV Screen apertures inmicrons 630 500400 315250 200160 100 %fal1through 99 98 97 95 94 25 9 1 This is quite similar to the granulometry of Table III of Example 3.

EXAMPLE 5 A prepolymerizer, a vertical autoclave of stainless steel with a capacity of 2 m5 equipped with a turbine agitator of 350 mm. diameter rotating at 700 rpm, received 1,700 kg. of vinyl chloride monomer and 96.36 g. of acetyl cyclohexanesulfonyl peroxide (ACSP) which provided 6.8 g. or 0.0004 percent of active oxygen. The reaction temperature was set at 55 C. and the internal pressure was 7.85 bars. Polymerization was for 1 hour minutes after which the catalyst was practically destroyed. This catalyst is of the type called rapid because it acts vigorously and decomposes rapidly. The yield was 9.2 percent of polymer and the polymerization had been arrested. This reaction mass was transferred to an autoclave of the type of FIG. 2 of 12 m. capacity. The helical agitator was rotated at 5 rpm. The prepolymerizer was rinsed with 500 kg. of the same monomer which was immediately transferred to the cylindrical autoclave. 1,200 kg. of monomer were introduced into the cylindrical autoclave together with 2,210 g. of lauroyl peroxide catalyst (0.065 percent of the total monomer). The reaction mass was rapidly raised to 55 C. at a pressure of 7.85 bars and the polymerization continued for 17 hours at the mild rate of agitation. The residual monomer was then vented. The yield was 70.3 percent of powdery polymer of apparent density 0.5 and K index (Fikentscher) of 68. The granulometry was:

TABLE V Screen apertures %fallthrough 99 99 99 98 9s 98 96 21 Seventy-five percent of the particles were between 100 and 160 microns and 96'percent less than 160 microns in size. This example further illustrates the manner in which the average size of the grains of the product can be controlled.

EXAMPLE 6 Polymerization continued for 15 hours 30 minutes at 55 C. with the same mild agitation. The yield was 73 percent of polymer having a density of 0.35 and a K value of 68. The granulometry was:

TABLEVI Screen apertures in microns 630 500 400 315 250 200 160 100 %fallthrough 97 96 94 92 62 22 0.5

In this case the density of the product was sharply reduced and the grain sizes are more widely dispersed, which is, for some purposes, not particularly desirable. These undesirable features can be eliminated, when only one-third of the monomer is prepolymerized, by using a higher speed of agitation than that employed in the two examples. For example doubling the velocity therein recited will produce results similar to Examples 3 and 4.

EXAMPLE 7 The apparatus was that of Example 5. The prepolymerizer was purged by vinyl chloride and then received 1,579.6 kg. of vinyl chloride, 120.4 kg. of vinyl acetate, and 96.36 g. of ACSP, which corresponds to 0.0004 percent of active oxygen. The temperature of the comonomer is raised to 62 C. which corresponds to an internal pressure of 9.3 bars. The reaction became inert at 1 hour 15 minutes and the conversion was about 9.5 percent. The reaction mass was transferred to the big autoclave. The prepolymerizer was rinsed with 500 kg. of vinyl chloride and added to the big autoclave, which also received 1,079.6 kg. of vinyl chloride and 120.4 kg. of vinyl acetate. It also received 612 g. of ADBN (slow catalyst). The reaction medium was rapidly raised to 62 C. which corresponded to 9.3 bars. The polymerization was continued 11 hours with the agitator at 5 rpm. After venting, a yield of 75.2 percent of the total monomer was received. It had a K value of 56 and an apparent density of 0.69. Its granulometry was:

TABLE VII Screen apertures in microns 630 500 400 315 250 200 160 %fallthrough 99 99 98 98 94 92 88 10 Seventy-eight percent of the particles were between 100 and 160 microns and 92 percent were less than 200 microns in size.

It is an object of this invention to control certain qualities of the new product, and its granulometry, at will and to this effect we have discovered that particular types of apparatus may be employed to achieve particularly desirable results, and that this is particularly true when the process involves the development of minute seeds in a small quantity of monomer and the regular enlargement of those seeds to spherical granules of commercially desirable sizes in a large body of monomer. It will be understood that in the term monomer we include single monomers and pluralities of compatible monomers, and that the compatibility of other monomers and vinyl chloride to form useful copolymers has been largely investigated and published elsewhere. The examples given herein are for illustrative purposes to demonstrate the applicability of the new process to the techniques of copolymerization.

The apparatus used in Examples 8, 9, l0, l1 and 12 included a prepolymerizer coupled to a rotary, cylindrical autoclave in the bottom of which was a line of loose metal balls which roll through the reaction mass as the autoclave turns keeping it in constant agitation while it is still liquid and fluidizing the product when it has passed into the granular, solid, phase.

These examples demonstrate particularly close control of the dimensions and granulometry of the polymers.

EXAMPLE 8 This example is for comparative purposes and describes the polymerization of vinyl chloride using a single catalyst, the prepolymerization being carried out on the entire monomer in the pressure of all the catalyst. A vertical prepolymerizer of l m. capacity, as illustrated in FIG. 1, received 825 kg. of vinyl chloride, after purging, and 150 g. (0.02 percent of the monomer) of ADBN. The agitator was of impeller type 220 mm. in diameter run at 720 r.p.m. The temperature was 62 C., the pressure 9.5 bars, and after 2 hours 45 minutes the reaction mass was transferred to a rotary autoclave, which was of 3 m5 capacity containing TABLE VIII Screen apertures in microns 630 500400 315 250 200160 100 %fallthrough 97 96 94 92 90 86 82 3.5

Eighty-two percent of the particles were of dimensions less than 160 microns.

EXAMPLE 9 The present invention was carried out in the apparatus of Example 8 under the following comparable conditions:

The prepolymerizer received 500 kg. of vinyl chloride, after purging, and 100 g. of ADBN 0.02 per cent). After 2 hours 45 minutes of prepolymerization the mass was transferred to the rotary autoclave which had already received 500 kg. of vinyl chloride, after purging. One-hundred g. of ADBN were added to the rotary autoclave (0.01 percent) and the temperature was established at 62 C. and 9.5 bars. Polymerization was continued for 11 hours 45 minutes, the autoclave was vented, and the yield was 69.8 percent of spherical granules having an apparent density of 0.55. The granulometry was:

TABLE IX Screen apertures in microns 630 500 400 315 250 200160 100 %fallthrough 99 99 98 97 90 85 2 The granulometry was concentrated in limited sizes, 85 percent of the particles being less than 160 microns and 83 percent between and microns.

EXAMPLE 10 Using the same apparatus, the process was carried out using a rapid catalyst (a catalyst of rapid decomposition) in the prepolymerizer and a slow catalyst (a catalyst of longlife) in the rotary autoclave.

The prepolymerizer received 500 kg. of vinyl chloride (about one-half), after purging, and 27.75 g. of ASCP, which furnished 0.0004 percent of active oxygen based on the weight of the monomer in the prepolymerizer. After 1 hour and 15 minutes of polymerization at 62 C. and 9.5 bars, the speed of the impeller being as aforesaid, the catalyst was exhausted and the reaction mass was transferred to the rotary autoclave, which had been purged and charged with 500 kg. of vinyl chloride and 200 g. of ADBN (0.02 percent of the reaction medium). Polymerization continued for 11 hours at 62 C., 9.5 bars pressure, and 8 r.p.m. The speed was reduced to 3 r.p.m., the apparatus was vented, and the product discharged with a yield of 70.2 percent of spherical granules of apparent density 0.55 and the following granulometry:

TABLE X Screen apertures in microns fallthrough If the results obtained in Examples 8, 9 and 10 be compared, it will be observed that an identical total polymerization was used and that the granulometry of the product of Example 10 was 88 percent less than 160 microns and 84 percent between 100 and 160 microns.

EXAMPLE 11 percent of active oxygen. After 1 hour 15 minutes of prepolymerization at 720 r.p.m., 62 C., and 9.5 bars, the catalyst became inert and the reaction mass was transferred to the purged rotary autoclave which had received 700 kg. of vinyl chloride and 140 g. of ADBN. The reaction proceeded for 12 hours at 62 C. and 9.5 bars at 8 r.p.m. The yield was 69.3 percent of spherical granules having an apparent density of 0.47 and the following granulometry:

TABLE XIa Screen apertures in microns fallthrough TABLE XIb Screen apertures inmicrons e30 500 400 315 250 200160 100 %fallthrough 99 99 99 9s 96 90 so 5 The apparent density was 0.47 but the grain sizes are more concentrated, 90 percent of the particles being less than 200 microns and 80 percent less than 160 microns and 75 percent between 100 and 160 microns.

EXAMPLE 12 The apparatus was that of Example 8 and FIG. 1. The prepolymerizer received 475 kg. of vinyl chloride and 25 kg. of vinyl acetate. The catalyst was ACSP of which 27.75 g. yielded 0.0004 percent of active oxygen. After 1 hour 15 minutes of polymerization at 720 r.p.m., 62 C. and 9.5 bars, the catalyst was inert and the reaction mass was transferred to the rotary autoclave which contained 475 kg. of vinyl chloride, 25 kg. of vinyl acetate, and 200 g. of ADBN (0.02 percent). The polymerization proceeded for hours at 62 C., 9.5 bars, and 8 r.p.m. for a total duration of reaction of l 1 hours minutes. The product had a yield of 73.2 percent, an apparent density of 0.66 and a K value of 56. The granulometry was:

TABLE XII Screen apertures in microns 630 500 400 315 250 200 I60 I00 %fallthrough 99 99 98 98 95 87 72 2 Eighty-seven percent of the particles were less than 200 microns and 70 percent between 100 and 160 IIIICI'OIIS.

In this process the prepolymerizer need not be of the type illustrated in the drawings, although that type is of excellent performance. It might also be of any of the types of cylindrical autoclave shown in the figures, although smaller and equipped for higher speeds. Equal speeds of different types of autoclave are not comparable in efiect. For instance, a speed of 720 r.p.m. in the propeller type impeller of FIG. 1 may be equivalent in turbulent effect to a speed of 100 r.p.m. in the paddle wheel of FIG. 3, and it may be mechanically difficult to attain equal violence with the rotary autoclave of FIG. 1. Consequently, in considering this invention we must consider the first stage to be a stage of high turbulence and the second to be of mild turbulence, but consistent with good temperature control and homogeneity of the reaction mass. In consequence the first autoclave will be of a type capable of assuring all necessary turbulence and the second of a type assuring minimum turbulence consistent with heat control. FIG. 1 shows a combination of desirable types, each efficient in its own operation.

Although the rotary autoclave of FIG. 1 serve their purpose efficiently, there is mechanical difficulty in constructing them particularly when they are of large size. It is consequently, desirable that equivalent results be attained by fixed autoclaves and this has been achieved in the present invention by the use of second stage autoclaves such as those of FIGS. 3 and 4. In FIG. 3 there is a central shaft 58 which has oppositely disposed arms carrying full length paddles nest to the walls of the autoclave. In FIG. 4 the construction is similar except that the paddles are not full length. The characteristics of these autoclaves differ from each other and from those of the autoclaves of FIGS. 1 and 2. Throughout the examples, for comparative purposes, we have used only one type of prepolymerizer and one set of standard conditions, which is not to be taken to constitute a limitation.

EXAMPLE 13 A vertical autoclave of 200 l. capacity of stainless steel, provided with a turbine type agitator was purged and received 170 kg. of vinyl chloride and 30.6 g. of ADBN. The temperature was 62 C., the pressure 9.5 bars, and the speed was 720 r.p.m. This is a comparative example in which the entire quantity of monomer was put into the prepolymerizer.

After 3 hours of polymerization the mixture of polymer suspended in monomer was transferred to a 500 1. stainless steel horizontal autoclave of the type shown in FIG. 3, the agitator of which was rotated at 30 r.p.m As the transfer began, cold water was circulated through the jacket of the horizontal autoclave to increase the pressure gradient and speed up the transfer, which took less than 1 minute. The valve was then closed between the autoclaves. The temperature was raised to 62 C. and polymerization continued 13 hours. The yield was percent of a spherical powder having a K value of 62 and an apparent density of 0.56. The granulometry was:

TABLEXIII Screen apertures in microns 630 500 400 315 250 200 160 100 %fallthrough -98 98 97 95 93 82 7 EXAMPLE14 The apparatus was the same as that used in Example 13. 100 kg. of vinyl chloride were admitted to the purged prepolymerizer with 20 g. of ADBN catalyst.

The reaction conditions and speeds were as in Example 13. After 2 hours 45 minutes of polymerization the reaction mass was transferred to the second autoclave and mixed with 100 kg. of vinyl chloride and 20 g. of ADBN. The speed of the paddle wheels was 30 r.p.m. The polymerization continued 12 hours 15 minutes longer. The yield was 71.8 percent of spherical granules of K value 62 and apparent density 0.55. The granulometry was:

TABLE XIV Screen apertures inmicrons 630 500400 315 250 200160 100 %fallthrough 99 99 98 97 95 93 90 l The granulometry was concentrated in dimensions between 100 and 160 microns, only 11 percent being dispersed in other sizes.

EXAMPLE 15 The apparatus was the same as in. Example 13. The prepolymerizer received 100 kg. of vinyl chloride and 5.55 g. of ACSP. The agitator rotated at 720 r.p.m., the temperature was 62 C., and the pressure 9.5 bars. After 1 hour 15 minutes the catalyzer had become inert and the polymerization mass was transferred to the autoclave of FIG. 3 where it was mixed with 100 kg. of vinyl chloride and 40 g. of ADBN. The speed of agitation was 30 r.p.m., the temperature 62 C. and the pressure 9.5 bars. The reaction continued for another 11 hours 30 minutes. After venting, the yield was 70.6 percent of a polymer having a K value of 62 and an apparent density of 0.56. The granulometry was:

TABLE XV Screen apertures inmicrons 630 500400 315 250 200160 100 %fallthrough 99 99 99 98 97 92 90 2 The following comparisons are noted: compared to Examples 13 and 14 the total time of reaction was less, providing higher utility for the apparatus employed. The granulometry in the present example was concentrated, 90 percent being less than 160 microns and 88 percent being between 100 and 160 microns.

EXAMPLE 16 The apparatus of Example 13 was used. The prepolymerizer received 70 kg. of vinyl chloride monomer and 3.885 g. of ACSP, rapid catalyst. After 1 hour 15 minutes of prepolymerization at 720 r.p.m., 62 C. and 9.5 bars the catalyst had become inert, the mass latent, and it was transferred to the second autoclave with 140 kg. of vinyl chloride and 42 g. of ADBN, slow catalyst. Reaction was continued for 12 hours 30 minutes at 62 C., 30 r.p.m. and 9.5 bars. The yield was 69.7 percent of a spherical product having apparent density 0.49 and the granulometry was:

TABLE XVla Screen apertures in microns 630 500400 315 250 200160 100 %fallthrough 99 98 98 97 92 78 22 4 The density was less than that of the polymers of Examples l3, l4 and 15, the granulometry was more dispersed, and the mean dimensions of the particles were greater, which is advantageous for some purposes.

The same process was carried out with the sole exception that the prepolymerizer agitator was driven at 1,440 r.p.m. The product had the following granulometry:

TABLE XVIb Screen apertures inmicrons 630 500 400 315 250 200160 100 %fallthrough 99 99 99 98 97 91 78- 4 The apparent density was 0.49. The product was dispersed in fewer sizes, 91 percent being less than 200 microns and 74 percent between 100 and 160 microns.

EXAMPLE 17 The apparatus was the same as in examples immediately preceding. The prepolymerizer received 95 kg. of vinyl chloride and 5 kg. of vinyl acetate. 5.5 g. of ACSP provided 0.0004 percent of active oxygen. After 1 hour 15 minutes of prepolymerization at 720 r.p.m., 62 C. and 9.5 bars, the rapid catalyst was inert, the reaction mass latent, and it was transferred to the second autoclave with 95 kg. of vinyl chloride and 5 kg. of vinyl acetate. 40 g. of ADBN were added (0.02 percent of the total charge). Reaction proceeded 10 hours 15 minutes at 62 C., 30 r.p.m. and 9.5 bars. The yield was 75.2 percent of a spherical product having an apparent density of 0.68 and a K value of 56. The granulometry was:

TABLE XVll Screen apertures in microns 630 500 400 315 250 200 160 %fallthrough 99 98 98 96 94 85 62 l Eighty-five percent of the particles were less than 200 microns and 61 percent were between 100 and microns.

EXAMPLE 18 The apparatus employed is the prepolymerizer of FIG. 1 and the fixed horizontal cylindrical autoclave of FIG. 4. The prepolymerizer was as described hereinabove being of 200 1. capacity of stainless steel equipped with a propeller type stirrer 180 mm. in diameter. It received kg. of vinyl chloride and 30.6 g. of ADBN. Prepolymerization was at 62 C., 710 r.p.m., 9.5 bars, and continued for 2 hours. The secondary autoclave was of 500 1. capacity having a stirrer as represented in FIG. 4. After the transfer, which took 1 minute, the polymerization continued under identical conditions for 14 hours at 8 r.p.m. The yield was 72.6 percent of a powder having a K value of 62 and an apparent density of 0.58. The granulometry was:

TABLE XVlIl Screen apertures inmicrons 630 500400 315 250 200 160100 %fallthrough 99.5 99 98 96 9634.5 27 1 This example was for comparative purposes.

3 EXAMPLE 19 The apparatus used was the same as that of Example 18 but the monomer was divided about in two. The prepolymerizer received 100 kg. of it and 20 g. of ADBN. Prepolymerization continued for 2 hours 30 minutes under the conditions of Example 18 and the reaction mass was transferred to the cylindrical autoclave where it received 100 kg. of monomer and 20 g. of ADBN. The agitator was rotated at 8 r.p.m. and the process continued for 12 hours 45 minutes. The product had a yield of 70.7 percent, a K value of 62, and an apparent density of 0.56. Its granulometry was:

TABLEXIX Screen apertures inmicrons 630 500 400 315 250 200160 100 %fallthrough 99 9s 9s 97 94 92 89 2 Compared to the product of Example 18 the concentration of sizes was much improved, 87 percent being between 100 and 160 microns. The product was composed of spheres. The advantage of growing the minute particles of polymer produced in the prepolymerizer in fresh monomer is apparent.

EXAMPLE 20 In this example the prepolymerization took place in the presence of a catalyst of rapid decomposition and the secondary stage of polymerization in the presence of a catalyst of slow decomposition. A prepolymerizer received 100 kg. of vinyl chloride and 5.55 g. of ACSP, providing 0.0004 percent of active oxygen based on the weight of the monomer fraction in the prepolymerizer. The speed was 710 r.p.m., the temperature 62 C. and the pressure 9.5 bars. After 1 hour 15 minutes the catalyst was inert and polymerization had ceased. The polymerization mass containing minute seeds of polymer in unpolymerized liquid monomer was transferred to the second autoclave and mixed with 100 kg. of vinyl monomer and 40 g. of ADBN. The agitator was driven at 8 r.p.m., the temperature was 62 C. and the pressure 9.5 bars. Polymerization continued 11 hours 15 minutes. The yield was 71.2 percent, the K value 62, and the apparent density 0.56. The granulometry was:

TABLEXX Screen apertures in microns 630 500 400 315 250 200 160 100 %fallthrough 99 99 99 97 96 93 89 1 If the results of Examples 18, 19 and 20 be compared, it will be observed that for identical yields the duration of the operation was less in Example 20 and that the granulometric concentration of sizes is equally good, 89 percent of particles being less than 160 microns and 88 percent between 100 and 160 microns.

EXAMPLE 21 The apparatus of Example 18 was used. The prepolymerizer received 70 kg. of vinyl chloride and 3.885 g. of ACSP. After 1 hour 15 minutes at 710 r.p.m., 62 C. and 9.5 bars, the rapid catalystwas substantially destroyed and the polymerization had ended. The mass was transferred to the other autoclave and mixed with 140 kg. of vinyl chloride. Forty-two grams of ADBN were added and the reaction continued at the same temperature, pressure and velocity of agitation for 12 hours 15 minutes. The yield was 69.4 percent having a density of 0.48 and a K value of 62. The granulometry was:

TABLE XXIa Screen apertures inmicrons 630 500400 315 250 200160 100 %fallthrough 98 98 98 96 91 20 3 The apparent density of the spherical particles was less and the sizes were more widely distributed.

In order to produce a more concentrated product, the identical process was carried out using 1,420 r.p.m., in the prepolymerizer. The granulometry was:

TABLE XXIb Screen apertures in microns 630 500 400 315 250 200 I60 100 %fallthrough 99 99 99 97 97 92 75 5 The density was 0.48.

EXAMPLE 22 Under identical conditions and in the same apparatus as Example 18, 95 kg. of vinyl chloride and 5 kg. of vinyl acetate were polymerized in the presence of a rapid catalyst yielding 0.0004 percent of active oxygen. After 1 hour 15 minutes this was mixed in the second autoclave with 95 kg. of vinyl chloride, 5 kg. of vinyl acetate, and 40 g. of a rapid catalyst providing 0.02 percent of the total weight of the charge. Reaction continued for 10 hours 15 minutes for a yield of 73.6 percent, a density of 0.66 and a K value of 56. The granulometry was:

TABLE XXII Screen apertures in microns 630 500 400 3 I 5 250 200 I60 lOO fallthrough 99 98 97 96 92 84 58 2 In the following examples the second stage autoclave was a fixed vertical cylinder having a spiral agitator of blade type rotating adjacent the wall in such a manner that it elevated the product from the bottom alongside the cold wall and transferred it inwardly to descend again along the axis of the cylinder.

EXAMPLE 23 V A vertical autoclave of 1,000 1. capacity, of stainless steel, having a 300 mm. impeller driven at 720 r.p.m. received 800 kg. of vinyl chloride and 144 g. (0.018 percent) of ADBN. The temperature was 62 C. and the pressure was 9.5 bars. After 2 hours of polymerization the mixture was transferred to the vertical autoclave which was of 2m. capacity provided with the vertical helical agitator and already contained 800 kg. of vinylchloride. The speed of the agitator was 10 r.p.m., the temperature was 62 C. and the pressure 9.5 bars. Polymerization continued for another 13 hours. The yield was 70.8 percent of spherical granules having a K value of 62 and an apparent density of 0.52. The granulometry was:

TABLE XXIII Screen apertures in microns 630 500 400 315 250 200 160 100 %fallthrough 99 98 98 98 97 93 90 1 An identical test at which the helical agitator was rotated at 5 r.p.m. produced a comparable result.

EXAMPLE 24 The apparatus of Example 23 received 500 kg. of vinyl chloride monomer and 100 g. of ADBN (0.02 percent). Other conditions were identical. After 2 hours of prepolymerization the mass was transferred to the second autoclave and mixed with 500 kg. of vinyl chloride and 100 g. of ADBN. The helical agitator was run at r.p.m. Other conditions were the same and the duration was 12 hours. The yield was 73.2 percent and the K value was 62 and the apparent density 0.62 of spherical granules, the granulometry of which was:

TABLE XXIV Screen apertures in microns 630 500 400 315 250 200 160 100 fallthrough 99 99 99 98 97 90 88 1 The density of the product was superior to that of Example 23 and the granulometry was about equally concentrated.

EXAMPLE 25 The prepolymerizer received 500 kg. of the same monomer and 27.75 g. of ACSP (0.0004 percent of active oxygen). The other conditions were identical with the preceding example. After 1 hour minutes the rapid catalyst and the process were inert and the charge was mixed with 500 kg. of vinyl chloride and 200 g. of ADBN in the second autoclave. The conditions were identical except that polymerization went 11 hours 15 minutes in addition to the time in the prepolymerizer. The yield was 72.8 percent, the K value 62 and the apparent density 0.63. The granulometry was:

TABLE XXV Screen apertures in microns 630 500 400 315 250 200 160 100 %fallthrough 99 99 98 98 98 93 91 2 For a yield approximately the same the total duration of the process of the present examples was less. The density of the products of Examples 24 and 25 was greater than that of Example 23.

EXAMPLE 26 The apparatus was the same as in the preceding example. The prepolymerizer received 350 kg. of vinyl chloride and 19.425 g. of ACSP. After 1 hour 15 minutes at 720 r.p.m., 62 C., and 9.5 bars, the reaction became latent and the mass was transferred to the second stage autoclave where it was mixed with 700 kg. of vinyl chloride and 210 g. of ADBN. The reaction continued 1 1 hours 45 minutes. The yield was 70.2 percent, the density was 0.50 and the K value 62. The granulometry was:

TABLEXXVIa SCI'CCI'I apertures inmicrons 630 500400 315 250 200160 100 %fallthrough 99 92 9s 97 92 so 25 2 The apparent density of the product of this example was inferior to that of the two preceding examples and the distribution of spheres more widely distributed in larger sizes, it being noted that the monomer subjected to prepolymerization represented onethird of the total monomer and that the speed of the prepolymerizer agitator was 720 r.p.m.

When the same example was carried out with a speed of 1,440 r.p.m in the prepolymerizer, the granulometry was:

TABLE XXVIb Screen apertures in microns 630 500 400 315 250 200160 100 %fallthrough 99, 99 99 98 90 80 1 The density was 0.5, the granulometry was more concentrated in smaller sizes.

EXAMPLE 27 The apparatus was as in the preceding example. The prepolymerizer received 475 kg. of vinyl chloride, 25 kg. of vinyl acetate, and 27.75 g. of ACSP (0.0004 percent) of active oxygen). After 1 hour 15 minutes of polymerization at 62 C., 9.3 bars and 720 r.p.m., the mass was transferred to the second stage autoclave and mixed with 475 kg. of vinyl chloride, 25 kg. of vinyl acetate and 200 g. of ADBN. The reaction proceeded 9 hours 45 minutes under the same conditions. The yield was 74.1 percent. The product had an apparent density of 0.69 and a K value of 56. The granulometry was:

TABLEXXVII Screen apertures inmicrons 630 500 400 315250 200160 100 %fallthrough 99 99 98 98 95 90 75 1 In the preceding description no attempt has been made to list the ethylenic monomers which can be polymerized by this process and in this apparatus. However, the process is applicable to all ethylenic monomers which can be polymerized by standard processes. It is particularly advantageous when applied to the polymerization of vinyl chloride in the presence of compatible monomers. It is to be understood that the process is polymerization in mass and is applicable to all monomers which can be polymerized in mass, that is to say in the absence of solvents and diluents.

Only a few catalysts have been used in the examples but that has been to provide comparative data. All catalysts which are useful in the mass polymerization of ethylenic monomers can be used in association with their monomer. For use with vinyl chloride the organic peroxide catalysts are preferred.

The preferred form of apparatus employs a prepolymerizer of the type shown in FIG. 1 but apparatus has been successfully constructed and operated with prepolymerizers of the type shown in FIGS. 2, 3 and 4. In comparing such different constructions, it is not proper to compare the speeds one with another because a speed of 1,000 r.p.m. with a turbine type impeller may have no more turbulent effect than a speed of r.p.m. with the paddle wheel of FIG. 3. The temperature employed in the process are those which are customarily used in the polymerization of ethylenic monomers in mass. Those given here are mean values for the polymerization of vinyl chloride. They are not to be considered limitations because polymerization by this process will proceed to superior results under comparable conditions. For compatible monomers polymerizable in mass, for lists of catalysts and conditions of reaction favorable to polymerization of such monomers in mass prior publications may be consulted.

As many apparently widely different embodiments of the present invention may be made without departing from the spirit and scope thereof, it is to be understood that the invention is not limited to the specific embodiments.

What is claimed is:

1. A method of polymerizing ethylenic monomers capable of polymerization in mass, to form spherical particles with controlled size distribution, which comprises subjecting an ethylenic monomer in mass to conditions of temperature, pressure, and catalysis favorable to polymerization in a locus provided with agitation of sufficient violence to achieve major turbulence in the reaction mass until about 7 to percent polymerization has been attained, the minute particles of polymer thus formed being suspended in liquid monomer, transferring the liquid suspension to another locus provided with mild agitation, mixing it with an additional body of monomer of at least substantially the same quantity as the original monomer, and continuing the polymerization in mass at a lower rate under conditions favorable to the growth of the particles, including agitation which is substantially milder than in the first locus and is a function of good temperature control and achieves at the most minor turbulence and conditions of temperature, pressure, and catalysis favorable to polymerization.

2. A method according to claim 1 in which the monomer comprises vinyl chloride.

3. A method according to claim 2 in which the monomer submitted to turbulent agitation is from about one-third to one-half of the total quantity of monomer employed in the process.

4. A method according to claim 1 which comprises selecting a turbulence of agitation in the first step of polymerization and thereby controlling the granulometry of the product.

5. A method according to claim 1 in which the first stage of polymerization includes a rapid catalyst and the second stage includes a slow catalyst.

6. A method according to claim 1 in which the monomer includes vinyl chloride and a compatible ethylenic monomer.

7. A method according to claim 6 in which the compatible monomer is vinyl acetate.

8. A method according to claim 2 in which the first stage of polymerization is carried out with turbulence equivalent to that produced by a turbine type agitator at many hundreds of rpm. and the second stage is carried out with turbulence equivalent to that produced by a blade type agitator rotating at less than rpm.

A method of polymerizing ethylenic monomers capable of polymerization in mass, to form spherical particles with controlled size distribution, which comprises subjecting an ethylenic monomer in mass to conditions of temperature, pressure, and catalysis favorable to polymerization in a reaction vessel provided with agitation of sufficient violence to achieve ma'or turbulence m the reaction mass untll about 7 to 1 percent polymerization has been attained, the minute particles of polymer thus formed being suspended in liquid monomer, transferring the liquid suspension to another reaction vessel provided with mild agitation, mixing it with an additional body of monomer of at least substantially the same quantity as the original monomer, and continuing the polymerization in mass at a lower rate under conditions favorable to the growth of the particles, including agitation which is substantially milder than in the first reaction vessel and is a function of good temperature control and achieves at the most minor turbulence and conditions of temperature, pressure, and catalysis favorable to polymerization, rinsing the reaction vessel with monomer, and adding the rinse to the partly polymerized mass in the second reaction vessel.

10. A method of polymerizing ethylenic monomers capable of polymerization in mass, to form spherical particles with controlled size distribution, which comprises subjecting an ethylenic monomer in mass to conditions of temperature, pressure, and catalysis favorable to polymerization in a reaction vessel provided with agitation of sufficient violence to achieve major turbulence in the reaction mass until about 7 to 15 percent polymerization has been attained, the minute particles of polymer thus formed being suspended in liquid monomer, transferring the liquid suspension to another reaction vessel provided with mild agitation, mixing it with an additional body of monomer of at least substantially the same quantity as the original monomer, and continuing the polymerization in mass at a lower rate under conditions favorable to the growth of the particles, including agitation which is substantially milder than in the first reaction vessel and is a function of good temperature control and achieves at the most minor turbulence and conditions of temperature, pressure, and catalysis favorable to polymerization, rinsing the reaction vessel with monomer, and adding the rinse to the partly polymerized mass in the second reaction vessel and adding a catalyst to the reaction liquid in the second reaction vessel.

11. A method according to claim 1 in which the catalyst employed in the first stage is of slow type and in quantity which exhausts itself before the polymerization exceeds about 15 percent.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTlON Patent NO. 3,687,919 Dated August 29, 1972 Inventor(s) JEAN CLAUDE THOMAS It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Title Page, Column 1, at "[30]", add March 18, 1965 France. .659756, March 19, 1965 France. .659915, March 32, 1965 France. .6510180, March 23, 1965 France. 651032 Signed and sealed this 6th day of March 1973.

(SEAL) Attest: I

EDWARD M.FLETCHER,JR. I ROBERT GOTTSCHALK Attesting Officer Commissioner of Patents USCOMM-DC GO37G-V69 n u s. covuumun rmnnm, ornc: 1969 0- and 

2. A method according to claim 1 in which the monomer comprises vinyl chloride.
 3. A method according to claim 2 in which the monomer submitted to turbulent agitation is from about one-third to one-half of the total quantity of monomer employed in the process.
 4. A method according to claim 1 which comprises selecting a turbulence of agitation in the first step of polymerization and thereby controlling the granulometry of the product.
 5. A method according to claim 1 in which the first stage of polymerization includes a rapid catalysT and the second stage includes a slow catalyst.
 6. A method according to claim 1 in which the monomer includes vinyl chloride and a compatible ethylenic monomer.
 7. A method according to claim 6 in which the compatible monomer is vinyl acetate.
 8. A method according to claim 2 in which the first stage of polymerization is carried out with turbulence equivalent to that produced by a turbine type agitator at many hundreds of r.p.m. and the second stage is carried out with turbulence equivalent to that produced by a blade type agitator rotating at less than 100 r.p.m.
 9. A method of polymerizing ethylenic monomers capable of polymerization in mass, to form spherical particles with controlled size distribution, which comprises subjecting an ethylenic monomer in mass to conditions of temperature, pressure, and catalysis favorable to polymerization in a reaction vessel provided with agitation of sufficient violence to achieve major turbulence in the reaction mass until about 7 to 15 percent polymerization has been attained, the minute particles of polymer thus formed being suspended in liquid monomer, transferring the liquid suspension to another reaction vessel provided with mild agitation, mixing it with an additional body of monomer of at least substantially the same quantity as the original monomer, and continuing the polymerization in mass at a lower rate under conditions favorable to the growth of the particles, including agitation which is substantially milder than in the first reaction vessel and is a function of good temperature control and achieves at the most minor turbulence and conditions of temperature, pressure, and catalysis favorable to polymerization, rinsing the reaction vessel with monomer, and adding the rinse to the partly polymerized mass in the second reaction vessel.
 10. A method of polymerizing ethylenic monomers capable of polymerization in mass, to form spherical particles with controlled size distribution, which comprises subjecting an ethylenic monomer in mass to conditions of temperature, pressure, and catalysis favorable to polymerization in a reaction vessel provided with agitation of sufficient violence to achieve major turbulence in the reaction mass until about 7 to 15 percent polymerization has been attained, the minute particles of polymer thus formed being suspended in liquid monomer, transferring the liquid suspension to another reaction vessel provided with mild agitation, mixing it with an additional body of monomer of at least substantially the same quantity as the original monomer, and continuing the polymerization in mass at a lower rate under conditions favorable to the growth of the particles, including agitation which is substantially milder than in the first reaction vessel and is a function of good temperature control and achieves at the most minor turbulence and conditions of temperature, pressure, and catalysis favorable to polymerization, rinsing the reaction vessel with monomer, and adding the rinse to the partly polymerized mass in the second reaction vessel and adding a catalyst to the reaction liquid in the second reaction vessel.
 11. A method according to claim 1 in which the catalyst employed in the first stage is of slow type and in quantity which exhausts itself before the polymerization exceeds about 15 percent. 